CMP(O) tripodands: synthesis, potentiometric studies and extractions
摘要:
含有三个羧甲基膦酸酯(CMP)或-膦氧化物(CMPO)基团的配体系统通过连接在三脚架平台上,已合成用于金属络合并从HNO3溶液中提取。结合到离子选择性电极(ISE)和苦味酸盐萃取中,与Na+、K+、Ag+、Ca2+、Cd2+、Hg2+、Pb2+、Cu2+、Eu3+和Fe3+的实验表明,CMPO三脚配体3对Eu3+非常选择性,并形成非常稳定的络合物(log βML = 28.3)。通过Eu3+和Am3+进行的液-液萃取显示CMP(O)三脚配体3、11和13在1,1,2,2-四氯乙烷中具有合理的萃取性能,而在1-辛醇中所有研究的三脚配体的分配系数都较低。在加入协同剂六溴化钴双(二碳硼烷)阴离子(溴-COSAN)后,CMP(O)三脚配体3和4对Am3+和Eu3+的萃取分配系数显著增加。共价连接的COSAN仅在0.001-0.01 M HNO3中增强Am3+和Eu3+的萃取。利用CMP(O)三脚配体功能化的树枝状磁性硅基粒子,导致从0.01 M HNO3溶液中有效去除Am3+和Eu3+的粒子(31和32)。
CMP(O) tripodands: synthesis, potentiometric studies and extractions
作者:Marta M. Reinoso-García、Dominik Jańczewski、David N. Reinhoudt、Willem Verboom、Elżbieta Malinowska、Mariusz Pietrzak、Clement Hill、Jiří Báča、Bohumír Grüner、Pavel Selucky、Cordula Grüttner
DOI:10.1039/b600412a
日期:——
Ligand systems containing three carbamoylmethylphosphonate (CMP) or -phosphine oxide (CMPO) moieties attached to a tripodal platform have been synthesized for metal complexation and subsequent extraction from HNO3 solutions. The incorporation into ion selective electrodes (ISE) and picrate extractions with Na+, K+, Ag+, Ca2+, Cd2+, Hg2+, Pb2+, Cu2+, Eu3+ and Fe3+ shows that CMPO tripodand 3 is very selective for Eu3+ and forms a very stable complex (log βML = 28.3). Liquid–liquid extractions performed with Eu3+ and Am3+ show reasonable extraction properties of the CMP(O) tripodands 3, 11 and 13 in 1,1,2,2-tetrachloroethane, while in 1-octanol for all tripodands studied the distribution coefficients are low. Upon addition of the synergistic agent hexabrominated cobalt bis(dicarbollide) anion (bromo-COSAN) the distribution coefficients for Am3+ and Eu3+ extraction increase considerably for CMP(O) tripodands 3 and 4. Covalently linked COSAN only enhances the extraction of Am3+ and Eu3+ at 0.001–0.01 M HNO3. The functionalization of dendrimer coated magnetic silica particles with CMP(O) tripodands led to very effective particles (31 and 32) for Am3+ and Eu3+ removal from 0.01 M HNO3 solutions.
含有三个羧甲基膦酸酯(CMP)或-膦氧化物(CMPO)基团的配体系统通过连接在三脚架平台上,已合成用于金属络合并从HNO3溶液中提取。结合到离子选择性电极(ISE)和苦味酸盐萃取中,与Na+、K+、Ag+、Ca2+、Cd2+、Hg2+、Pb2+、Cu2+、Eu3+和Fe3+的实验表明,CMPO三脚配体3对Eu3+非常选择性,并形成非常稳定的络合物(log βML = 28.3)。通过Eu3+和Am3+进行的液-液萃取显示CMP(O)三脚配体3、11和13在1,1,2,2-四氯乙烷中具有合理的萃取性能,而在1-辛醇中所有研究的三脚配体的分配系数都较低。在加入协同剂六溴化钴双(二碳硼烷)阴离子(溴-COSAN)后,CMP(O)三脚配体3和4对Am3+和Eu3+的萃取分配系数显著增加。共价连接的COSAN仅在0.001-0.01 M HNO3中增强Am3+和Eu3+的萃取。利用CMP(O)三脚配体功能化的树枝状磁性硅基粒子,导致从0.01 M HNO3溶液中有效去除Am3+和Eu3+的粒子(31和32)。